Carbonaceous complex structure and manufacturing method therefor

ABSTRACT

A carbonaceous complex structure in which a fullerene thin film is used as a part of the constituent material to improve adhesion between neighboring layers to enable a solar cell or a sensor to be produced to high strength, and a method for manufacturing the carbonaceous complex structure, are disclosed. The carbonaceous complex structure includes a substrate  1  of quartz or glass, on which are layered a carbonaceous thin film  2  and a fullerene thin film  3.  Thermal decomposition of an organic compound is used for forming the carbonaceous thin film  2,  while a method for vapor-depositing or polymerizing fullerene is used for forming the fullerene thin film  3.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional Patent Application under 37 CFR 1.53(b)based on Parent application Ser. No. 09/598,304, filed Jun. 21, 2000,which claims priority to Japanese Application Nos: P11-179290, filedJun. 25, 1999 and P2000 005116, filed Jan. 14, 2000.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a carbonaceous complex structure employing afullerene based thin film, and a manufacturing method therefor.

2. Description of Prior Art

Recently, a sensor device, comprising a carbonaceous thin film and athin film of a heterogeneous material from it, both layered on asubstrate, has been developed in order to exploit characteristics properto the carbonaceous thin film, such as electric conductivity.

OBJECT AND SUMMARY OF THE INVENTION

It is an object of the present invention to provide a carbonaceouscomplex material comprising the above-described carbonaceous thin filmin combination with a fullerene thin film for improving adhesion betweenneighboring layers and for realizing peculiar optical properties, suchas charge separation capability.

In one aspect, the present invention provides a carbonaceous complexstructure comprising a layered set of a substrate, a carbonaceous thinfilm and a fullerene thin film.

In another aspect, the present invention provides a method formanufacturing a carbonaceous complex structure including a step offorming a carbonaceous thin film on a substrate by pyrolysis of anorganic compound and a step of forming a fullerene thin film.

In the carbonaceous complex structure of the present invention, sincethe carbonaceous thin film and the fullerene thin film (fullerenevapor-deposited film or fullerene polymer film as explained later indetail), layered on substrate, are both formed of carbon, and aresuperior in affinity to each other, adhesion between the two filmsdemonstrate is strong. The smoother the substrate surface, the morestrongly the carbonaceous thin film can be affixed to the substrate,thus providing a dense film exhibiting high mechanical strength.Therefore, the carbonaceous thin film can be bonded strongly to thefullerene thin film layered thereon.

On the other hand, in the carbonaceous complex structure of the presentinvention, the carbonaceous thin film exhibits superior electricalconductivity on the order of 10−2 S/cm. If a fullerene thin film isdeposited thereon, this fullerene thin film has valence band edge lowerby approximately 2.0 eV than that of the valence band edge of thecarbonaceous thin film and is able to operate as a donor/acceptor topermit charge separation by photo absorption. So, the carbonaceouscomplex structure finds application as a solar cell. Moreover, since thecarbonaceous complex structure has its electrical conductivity changedclearly with respect to a substrate, it finds latent usage as a sensordevice having superior durability with respect to the gas or thepressure.

The carbonaceous complex structure, having this superior effect, may beproduced by the above-defined method according to the present invention.

The manufacturing method according to the present invention, including astep of forming a carbonaceous thin film and a fullerene thin film on asubstrate, can be carried out easily because of a smaller number ofsteps to produce the carbonaceous complex structure efficiently.

Specifically, with the carbonaceous complex structure of the presentinvention, the carbonaceous thin film and the fullerene thin film, bothlayered on a substrate, are both formed of carbon and hence exhibit highaffinity so that the two films exhibit high adhesion to each other.

Moreover, the smoother the substrate surface, the more strongly can thecarbonaceous thin film be bonded thereto to form a dense film of highmechanical strength. In addition, the carbonaceous thin film surface canbe a smooth surface to profile the substrate surface, while it can bebonded strongly to the fullerene thin film deposited thereon.

With the carbonaceous complex structure of the present invention, havingthe above-mentioned layered structure, permits charge separation byphoto absorption and is able to form a so-called donor-acceptorheterojunction. Moreover, it has its electrical conductivity definitelychanged with respect to the substrate and hence finds application as asolar cell or sensor of high durability.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1C show the cross-sectional surfaces of a carbonaceous thinfilm according to the present invention, where FIG. 1A shows athree-layered structure, FIG. 1B shows a five-layered structure and FIG.1C shows a four-layered structure fitted with a light-transmittingelectrode.

FIG. 2 schematically shows the molecular structure of C₆₀.

FIG. 3 schematically shows the molecular structure of C₇₀.

FIG. 4 shows an exemplary structure of a C₆₀ vapor-deposited film.

FIG. 5 shows an exemplary structure of a C₆₀ polymer.

FIG. 6 shows an exemplary structure of a C₆₀ polymer film.

FIG. 7 shows another dimeric structure of another C₆₀ molecule.

FIG. 8 shows still a dimeric structure of another C₆₀ molecule.

FIG. 9 shows another dimeric structure of another C₆₀ molecule[C₁₂₀(b)].

FIG. 10 shows another dimeric structure of a C₆₀ molecule [C₁₂₀(c)].

FIG. 11 shows another dimeric structure of a C₆₀ molecule [C₁₂₀(d)].

FIG. 12 shows a structure of a C₁₁₈ molecule felt to be generated in thefullerene polymer generating process.

FIG. 13 shows a structure of a C₁₁₆ molecule felt to be generated in thefullerene polymer generating process.

FIG. 14 shows a numbering system of a C₇₀ molecule.

FIG. 15 shows a dimeric structure of a C₇₀ molecule felt to be producedin the fullerene polymerization process [C₁₄₀(a)].

FIG. 16 shows another dimeric structure of a C₇₀ molecule felt to beproduced in the fullerene polymerization process [C₁₄₀(b)].

FIG. 17 shows still another dimeric structure of a C₇₀ molecule[C₁₄₀(c)].

FIG. 18 shows still another dimeric structure of a C₇₀ molecule[C₁₄₀(d)].

FIG. 19 shows still another dimeric structure of a C₇₀ molecule[C₁₄₀(e)].

FIG. 20 shows still another dimeric structure of a C₇₀ molecule[C₁₄₀(f)].

FIG. 21 shows still another dimeric structure of a C₇₀ molecule[C₁₄₀(g)].

FIG. 22 shows still another dimeric structure of a C₇₀ molecule[C₁₄₀(h)].

FIG. 23 shows still another dimeric structure of a C₇₀ molecule[C₁₄₀(i): D2h symmetrical].

FIG. 24 shows still a dimeric structure of a C₇₀ molecule.

FIG. 25 shows a dimeric structure of a C₇₀ molecule [C₁₃₆(a)].

FIG. 26 shows another dimeric structure of a C₇₀ molecule [C₁₃₆(b)].

FIG. 27 shows still another dimeric structure of a C₇₀ molecule[C₁₃₆(c)].

FIG. 28 shows still another dimeric structure of a C₇₀ molecule[C₁₃₆(d)].

FIG. 29 shows still another dimeric structure of a C₇₀ molecule[C₁₃₆(e)].

FIG. 30 shows still another dimeric structure of a C₇₀ molecule[C₁₃₆(f)].

FIG. 31 shows still another dimeric structure of a C₇₀ molecule[C₁₃₆(g)].

FIG. 32 shows still another dimeric structure of a C₇₀ molecule[C₁₃₆(h)].

FIG. 33 shows still another dimeric structure of a C₇₀ molecule[C₁₃₆(i)].

FIG. 34 shows another dimeric structure of a C₇₀ molecule.

FIG. 35 shows a device for manufacturing fullerene molecules by arcdischarge.

FIG. 36 shows a manufacturing apparatus for manufacturing fullerenemolecules by a plasma polymerization method.

FIG. 37A shows the formation of a vapor-deposited film of fullerenepolymer film and

FIG. 37B shows the formation of a fullerene polymer film y illuminationof electromagnetic waves.

FIG. 38 shows a vapor deposition device.

FIG. 39 shows a high frequency plasma polymerization device.

FIG. 40 shows a device for manufacturing fullerene molecules by amicro-wave polymerization method.

FIG. 41 shows a device for manufacturing a fullerene polymer film by anelectrolytic polymerization method.

FIG. 42 is a schematic view showing a device for forming a carbonaceousthin film used in an embodiment of the present invention.

FIG. 43 shows a graph showing a spectrum of an example of a carbonaceousthin film.

FIG. 44 is a graph showing the spectrum of a carbonaceous thin film whenthe laser power is changed.

FIG. 45 is a graph showing the spectrum of a carbonaceous thin film whenthe laser power is further changed.

FIG. 46 is an X-ray diffraction diagram of a carbonaceous thin film.

FIG. 47 shows Raman measurements for a carbonaceous thin film.

FIG. 48 shows an image of a tapping mode AFM of a carbonaceous thinfilm.

FIG. 49 shows surface roughness of the image shown in FIG. 46.

FIG. 50 shows a photoelectron emission spectrum of a carbonaceous thinfilm.

FIG. 51 shows measured results of electrical conductivity.

FIG. 52 shows the relationship between the absorption coefficients ofthe carbonaceous thin film and the electrical conductivity.

FIG. 53 shows a tapping mode AFM image of a C₆₀ plasma polymer film.

FIG. 54 shows the photoelectron emission spectrum of a C₆₀ plasmapolymer film, a C₆₀ electrolytic polymer film and a C₆₀ vapor-depositedfilm.

FIG. 55 is an I-V graph on light illumination on a carbonaceous complexstructure according to the present invention.

FIG. 56 is a schematic view showing a device for forming a C₆₀vapor-deposited film used in another embodiment of the presentinvention.

FIG. 57 is a Raman spectrum diagram of a fullerene polymer filmaccording to the present invention.

FIG. 58 shows a C 1s XPS spectrum of the fullerene polymer film.

FIG. 59 is a peak analysis diagram of the C 1s XPS spectrum of thefullerene polymer film.

FIG. 60 shows a XPS spectrum showing a shakeup satellite area of thefullerene polymer film.

FIG. 61 shows a XPS valence band XPS of the fullerene polymer film.

FIG. 62 shows a TOF-MS spectrum of a fullerene polymer film obtained onplasma processing.

FIG. 63 shows a TOF-MS spectrum of a fullerene polymer film obtained onplasma processing.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

A functional element of the present invention may be a carbonaceouscomplex structure comprising a layered structure of a substrate, acarbonaceous thin film and the above-mentioned fullerene polymer film.

With this carbonaceous complex structure, in which the carbonaceous thinfilm and the fullerene polymer film, layered on a substrate, are bothformed substantially of carbon, the two films exhibit good affinity andadhere to each other satisfactorily.

Moreover, the smoother the surface of a substrate, the more strongly thecarbonaceous thin film is bonded to the substrate, with the thin filmbeing of a dense structure and a high mechanical strength, with the filmsurface being smooth to follow the substrate surface, thus assuringoptimum adhesion of the carbonaceous thin film with respect to thefullerene polymer film layered thereon.

In addition, in the carbonaceous complex structure, the carbonaceousthin film exhibits optimum electrical conductivity of e.g.,approximately 10⁻² S/cm. If the fullerene polymer film is layeredthereon, charge separation by photoelectric induction is possible sincethe fullerene polymer film has an edge of a valance band edge lower byapproximately 2.0 eV than that of the valence band of the carbonaceousthin film and operates as a donor/acceptor, so that the carbonaceouscomplex structure finds application as a solar cell. Moreover, thecarbonaceous complex structure is definitely changed in its electricalconductivity with respect to the substrate so that it finds crucialapplication as a sensor device having superior durability with respectto the gas or the pressure.

The carbonaceous complex structure, having the above-mentioned favorableresults, can be manufactured by a variety of different manufacturingmethods, as will be explained subsequently in detail.

Specifically, the present manufacturing method can be carried outreadily because of a smaller number of process steps to produce thecarbonaceous complex structure efficiently.

The carbonaceous complex structure of the present invention preferablycomprises a substrate 1 of e.g., quartz glass, and a carbonaceous thinfilm 2 and a fullerene polymer film 3, made up fullerene vapor-depositedfilm or a fullerene polymer film, layered on the substrate 1, as shownin FIG. 1A. With such structure, carriers produced in the fullerene thinfilm 3 or carriers in the substrate 1, in actuality implanted from anelectrode, are readily migrated into the carbonaceous thin film 2, thusimproving charge mobility.

If, in particular, the carbonaceous complex structure is used as a solarcell, it is preferred to provide a counter-electrode 4 of e.g., metal,on the substrate 1 in contact with the carbonaceous thin film 2 and toprovide a light transmitting electrode 5 of, e.g., ITO (indium oxidesdoped with tin) on the fullerene thin film 3. With such structure,charge separation by photoelectric induction is possible to open auseful application of the structure for a solar cell or a light emittingdiode.

If in particular the structure is used as a gas or pressure sensor, itis preferred to provide a pair of electrodes 5 a, 5 b, such ascomb-shaped electrodes, on the carbonaceous thin film 2, and to formfullerene thin film 3 between these electrodes 5 a, 5 b. Meanwhile, theelectrodes 5 a, 5 b may also be provided on the fullerene thin film 3.If the fullerene thin film 3 is bonded to the substrate, it is elevatedin electrical conductivity even at room temperature so that it can beused as a substrate temperature sensor by measurement of the electricalresistance.

As the materials for the light transmitting electrode 5 or theelectrodes 5 a, 5 b, the above-mentioned ITO (indium oxide doped withtin) is generally desirable. However, thin films of gold, silver,platinum or nickel may also be used.

The materials of the counter-electrode 4 may be enumerated by metals,such as aluminum, magnesium, indium alloys thereof and ITO.

These electrodes can be prepared by techniques, such as vapordeposition, sputtering, electron guns or electrolytic plating.Meanwhile, if materials other than ITO are used for thelight-transmitting electrodes, it is crucial to reduce the filmthickness further to assure light transmittance.

Our investigations have revealed that a smoother surface of thesubstrate 1 contacting the carbonaceous thin film 2, specifically, thesurface of the substrate 1 with roughness (average surface roughness(Ra)) of not higher than 1 μm is desirable. If the surface roughness isoutside this range, the carbonaceous thin film 2 exhibits onlyinsufficient adhesion to the substrate 1, thus possibly decreasingmechanical strength.

The substrate 1 may not only be a sole substrate of quartz glass orsilicon but also a composite substrate comprising the sole substrate andan electrically conductive layer of e.g., metal formed thereon.

As means for smoothing the substrate surface, known mechanical grinding,chemical surface processing or physical surface processing, may be used.

According to the present invention, pyrolysis (thermal CVD) of acarbon-containing organic compound is applied. Alternatively, avaporizable inorganic material can be deposited as a thin carbonaceousfilm, on vaporization, and can be used for the present invention.

This method thermally decomposes an organic compound in a gaseous phase,using a heating device, such as an electrical furnace, a high-frequencyfurnace etc. Specifically, the gaseous organic compound, entrained in acarrier gas, is introduced into a heating device housing a substratetherein, to heat the substrate to a temperature usually of 600 to 2000°C. and preferably to 700 to 1200° C. By so doing, the organic compoundis thermally decomposed to form a carbonaceous thin film composedessentially of carbon on the substrate.

Examples of the organic compounds include aromatic hydrocarbons, such astoluene or aniline, derivatives thereof, alkanes, such as methane,ethane or propane, alkines, such as acetylene, aliphatic hydrocarbons,such as hexane or oxane, heterocyclic compounds, such as furane,dioxane, thiophene or pyridine, and carbon compounds, such as fullerenemolecules. Two or more of these may be used in combination. Meanwhile,if safety in handling poses a problem in using these organic compounds,it is desirable to use organic compounds as low in toxicity as possible.

As the carrier gas, inert gases, such as nitrogen or argon, or a mixturethereof with hydrogen, is preferred.

The carbonaceous thin film, so formed, presents a fine smooth surface,as does a smooth substrate surface, with the film surface being asolver-white mirror surface. Stated differently, the adhesion andfilm-forming performance of a carbonaceous thin film according to thepresent invention tend to be affected appreciably by surface propertiesof a substrate.

Moreover, the carbonaceous thin film is a dense, hard and elastic film,with the Vickers hardness being not less than 500. The thin film can beused even as a diaphragm for a speaker.

In addition, the carbonaceous thin film has characteristics intermediatebetween those of a graphite exhibiting the behavior as metal and thoseof amorphous carbon exhibiting electrical conductivity comparable tothat of a semiconductor, with the electrical conductivity showingextremely low temperature dependency. Moreover, since the film has asmall band gap and the film contains graphite-like small fragments, ithas high electrical conductivity, with the electrical conductivity beingapproximately 10⁻² S/cm.

The fullerene thin film, deposited in contact with the carbonaceous thinfilm, means a fullerene vapor-deposited film or a fullerene polymerfilm. Of these, the latter is preferably used in view of film strengthand durability. The fullerene vapor-deposited film has an electricalconductivity of approximately 10⁻¹³ S/cm, with the level of the valenceelectron band being lower approximately 2.0 eV than that of thecarbonaceous thin film. The fullerene polymer film has an electricalconductivity of approximately 10⁻¹¹ to 10⁻⁷ S/cm, with the valenceelectron band level being higher by 0.7 eV than fullerene. With thevapor-deposited film, its characteristics in evaluation in atmospheretends to be lost in about one day, however, if in a polymer form, itscharacteristics are scarcely changed even in one month.

The respective films are formed from fullerene molecules as a startingmaterial. Since this material fullerene has only recently beendeveloped, it is more proper to date back to discovery of fullerenemolecules rather than directly entering into discussions of thefilm-forming method or the polymerization method.

Fullerene is a series of carbon compounds composed only of carbon atoms,as is diamond or graphite. The existence of fullerene was confirmed ineighties. That is, it was found in 1985 in a mass analysis spectrum of acluster beam by laser ablation of carbon. It was, however, five yearslater that the manufacturing method in reality was established.Specifically, a manufacturing method for fullerene (C₆₀) by arcdischarge of a carbon electrode was first found in 1990. Since then,fullerene is attracting notice as a carbonaceous semiconductor material(see Kratschmer, W., Fostiropoulos, K, Huffman D. R. Chem. Phys. Lett.1990, 170, 167. Kratschmer, W. Lamb L. D., Fostiropoulod. K, Huffman, D.R. Nature 1990, 347,354).

26.

Fullerene is a spherical carbon C_(n) (n=60, 70, 76, 78, 80, 82, 84, . .. ) which is a molecular aggregate resulting from spherical aggregationof an even number not less than 60 of carbon atoms. Representatives ofthe fullerenes are C₆₀ with 60 carbon atoms and C₇₀ with 70 carbonatoms. The C₆₀ fullerene has a molecular structure of what may be termeda soccer ball type in which its 60 apices are all occupied by carbonatoms. On the other hand, C₇₀ has what may be termed a rugby ball typemolecular structure, as shown in FIG. 3.

27.

In a C₆₀ crystal, C₆₀ molecules are arranged in a face-centered cubicstructure. It has a band gap of approximately 1.6 eV and may be deemedas a semiconductor. In an intrinsic state, it has an electricalresistivity of approximately 10⁷ Ω/cm. It has a vapor pressure ofapproximately 1 m Torr at 500° C. and, on sublimation, is capable ofvapor depositing a thin film. Not only C₆₀ but other forms of thefullerene are readily vaporized in vacuum or under reduced pressure andhence are able to yield an evaporated film easily.

However, the molecules of fullerene forms, such as C₆₀ or C₇₀, the mostmass-producible, are of zero dipole moment, such that evaporated filmsproduced therefrom are fragile in strength, because only the Van derWaal's force acts between its molecules. Thus, if the evaporated film isexposed to air, molecules of oxygen or water tend to be diffused andintruded into the gap between the fullerene molecules (FIG. 4), as aresult of which the evaporated film is not only deteriorated instructure but adverse effects may be occasionally produced in itselectronic properties. This fragility of the fullerene poses a problemin reference to device stability when applying the fullerene tofabrication of a thin-film electronic device.

For overcoming the weak points the fullerene polymer film, describedabove, the method of producing a so-called fullerene polymer consistingin polymerizing fullerene molecules has been proposed. Typical of thesemethods is a method of forming a fullerene polymer film by lightexcitation [see (a) Rao, A. M., Zhou, P, Wang., K. A, Hager., G. T.,Holden, J. M., Wang, Y., Lee, W. T., Bi, X, X., Eklund, P. C., Cornet,D. S., Duncan, M. A., Amster, J. J. Science 1993, 256995, (b) Cornet, D.C., Amster I. J., Duncan, M. A., Rao A. M., Eklund P. C., J. Phys. Chem.1993, 97,5036, (c) Li. J., Ozawa, M., Kino, N, Yoshizawa, T., Mitsuki,T., Horiuchi, H., Tachikawa, O; Kishio, K., Kitazawa, K., Chem. Phys.Lett. 1994, 227, 572].

In these methods, in which light is illuminated on a previously formedevaporated fullerene film, numerous cracks tend to be formed in the filmsurface due to volumetric contraction produced on polymerization, sothat produced films are problematic in strength. Moreover, it isextremely difficult to form a uniform thin film of a large surface area.

It has also been known to apply pressure or heat to fullerene moleculesor to cause collision of fullerene molecules against one another. It ishowever difficult to produce a thin film, even though it is possible toform a film (see, for a molecule collision method, (a) Yeretzian, C.,Hansen, K., Diedrich, F., Whetten, R. L., Nature 1992,359,44, (b)Wheten, R. L., Yeretzian, C., Int. J. Multi-layered optical disc. Phys.1992, B6,3801, (c) Hansen, K., Yeretzian, C., Whetten, R. L., Chem.Phys. Lett. 1994, 218,462, and (d) Seifert, G., Schmidt, R., Int. J.Multi-layered optical disc. Phys. 1992, B6,3845; for an ion beam method,(a) Seraphin, S., Zhou, D., Jiao, J. J. Master. Res. 1993, 8,1995, (b)Gaber, H., Busmann, H. G., Hiss, R., Hertel, I. V., Romberg, H., Fink,J., Bruder, F., Brenn, R. J. Phys. Chem., 1993,97,8244; for a pressuremethod, (a) Duclos, S. J., Brister, K., Haddon, R. C., Kortan, A. R.,Thiel, F. A. Nature 1991,351,380, (b) Snoke, D. W., Raptis, Y. S.,Syassen, K. 1 Phys. Rev. 1992, B45, 14419, (c) Yamazaki, H., Yoshida,M., Kakudate, Y., Usuda, S., Yokoi, H., Fujiwara, S., Aoki, K., Ruoff,R., Malhotra, R., Lorents, D. J., Phys. Chem. 1993,97,11161, and (d)Rao, C. N. R., Govindaraj, A., Aiyer, H. N., Seshadri, R. J. Phys. Chem.1995, 99,16814).

Noteworthy as a fullerene polymerization method or film-forming method,which should take the place of the above-enumerated fullerenepolymerization methods, is the plasma polymerization method or themicro-wave (plasma) polymerization method, previously proposed by thepresent inventors in e.g., Takahashi, N., Dock, H. or in Matsuzawa, N.,Ata M. J., Appl. Phys. 1993, 74,5790. The fullerene polymer film,obtained by these methods (see FIGS. 5 and 6), are thin films producedby polymerization of the fullerene molecules through an electronicexcited state. It is appreciably increased in strength in comparisonwith the evaporated thin fullerene film, dense and high in pliability.Since the fullerene polymer film is scarcely changed in its electronicproperties in vacuum or in air, it may be premeditated that its densethin-film properties effectively suppress diffusion or intrusion ofoxygen molecules into the inside of the film. In reality, generation offullerene polymer consisting the thin film by these methods may bedemonstrated by the time-of-flight mass spectrometry.

Irrespective of the type of the plasma method, electron properties of afullerene polymer film possibly depend appreciably on its polymerizationconfiguration. In reality, the results of mass spectrometry of the C₆₀polymer film, obtained by the micro-wave plasma method, bear strongresemblance to those of the C₆₀ argon plasma polymer thin film,previously reported by the present inventors [see Ata, M., Takahashi,N., Nojima, K., J. Phys. Chem. 1994, 98, 9960, Ata, M., Kurihara, K.,Takahashi, J. Phys., Chem., B., 1996, 101,5].

The structure of the fullerene polymer may be estimated by the pulselaser excited time-of-flight mass spectrometry (TOF-MS). In general,there is known a matrix assist method as a method for non-destructivelymeasurement the high molecular polymer. However, lacking the solventcapable of dissolving the fullerene polymer, it is difficult to directlyevaluate the actual molecular weight distribution of the polymer. Evenwith the mass evaluation by Laser Desorption Ionization Time-of-FightMass Spectroscopy (LDITOF-MS), it is difficult to make correctevaluation of the mass distribution of an actual fullerene polymer dueto the absence of suitable solvents or to the reaction taking placebetween C₆₀ and the matrix molecule.

The structure of the C₆₀ polymer can be inferred from the profile of adimer or the peak of the polymer of LDITOF-MS, as observed in theablation of such a laser power as not to cause polymerization of C₆₀.For example, LDITOF-MS of a C₆₀ polymer film, obtained with a plasmapower of e.g., 50 W, indicates that the polymerization of C₆₀ moleculesis most likely to take place through a process accompanied by loss offour carbon atoms. That is, in the mass range of a dimer, C₁₂₀ is aminor product, whilst C₁₁₆ is produced with the highest probability.

According to semi-empiric C₆₀ dimer calculations, this C₁₁₆ may bepresumed to be D2h symmetrical C₁₁₆ shown in FIG. 7. This may beobtained by C₅₈ recombination. It is reported that this C₅₈ is yieldedon desorption of C₂ from the high electronic excited state including theionized state of C₆₀ [(a) Fieber-Erdmann, M., et al., Phys. D. 1993,26,308 (b) Petrie, S. et al., Nature 1993,356,426 and (c) Eckhoff, W.C., Scuseria, G. E., Chem. Phys. Lett. 1993, 216,399].

If, before transition to a structure comprised of two neighboringfive-membered rings, this open-shell C₅₈ molecules are combined with twomolecules, C₁₁₆ shown in FIG. 7 is produced. However, according to thenotion of the present inventors, it is after all the [2+2] cycloadditionreaction by the excitation triplex mechanism in the initial process ofthe C₆₀ plasma polymerization. The reaction product is shown in FIG. 8.On the other hand, the yielding of C₁₁₆ with the highest probability asmentioned above is possibly ascribable to desorption of four sp³ carbonsconstituting a cyclobutane of (C₆₀)² yielded by the [2+2] cycloadditionfrom the excited triplet electronic state of C₆₀ and to recombination oftwo C₅₈ open-shell molecules, as shown in FIG. 8.

If a powerful pulsed laser light beam is illuminated on a C₆₀ finecrystal on an ionization target of TOF-Ms, as an example, polymerizationof fullerene molecules occurs through the excited electronic state, asin the case of the micro-wave plasma polymerization method. At thistime, ions of C₅₈, C₅₆ etc are also observed along with peaks of the C₆₀photopolymer.

However, since no fragment ions, such as C₅₈ ²⁺ or C²⁺ are observed,direct fragmentation from C₆₀ ³⁺ to C₅₈ ²⁺ and to C²⁺, such as isdiscussed in the literature of Fieber-Erdmann, cannot be thought tooccur in this case. Also, if C₆₀ is vaporized in a C₂F₄ gas plasma toform a film, only addition products of fragment ions of F or C₂F₄ of C₆₀are observed in the LDITOF-MS, while no C₆₀ polymer is observed. Thus,the LDITOF-MS, for which no C₆₀ polymer is observed, has a feature thatno C₅₈ nor C₅₆ ions are observed. These results of observation supportthe fact that C₂ loss occurs through a C₆₀ polymer.

The next problem posed is whether or not the C₂ loss is directly causedfrom 1, 2-(C₆₀)₂ produced by the [2+2] cycloaddition reaction shown inFIG. 8. Murry and Osawa et al proposed and explained the process ofstructure relaxation of 1,2-(C₆₀) 2 as follows [(a) Murry, R. L. et al,Nature 1993, 366,665, (b) Strout, D. L. et al, Chem. Phys. Lett. 1993,214,576, Osawa, E, private letter].

Both Murry and Osawa state that, in the initial process of structurerelaxation of 1,2-(C₆₀)₂, shown in FIG. 8, C₁₂₀ (d) of FIG. 11 isproduced through C₁₂₀ (b) of FIG. 8, resulting from cleavage of the1,2-C bond, having the maximum pinch of the cross-linked site, from C₁₂₀(c) of FIG. 10 having the ladder-like cross-linking by Stone-Walestransition (Stone, A. J., Wales, D. J., Chem. Phys. Lett. 1986, 128,501, (b) Saito, R. Chem. Phys. Lett. 1992, 195,537). On transition from1,2-(C₆₀)2 of FIG. 8 to C₁₂₀ (b) of FIG. 9, energy instability occurs.However, on further transition from C₁₂₀ (c) of FIG. 10 to C₁₂₀ (d) ofFIG. 11, the stabilized state is restored.

Although it is not clear whether the nC₂ loss observed in thepolymerization of C60 by plasma excitation directly occurs from1,2-(C₆₀) of FIG. 8 thought to be its initial process or after certainstructure relaxation thereof, it may be premeditated that the observedC₁₁₈ assumes the structure shown in FIG. 12 by desorption of C₂ fromC₁₂₀ (d) of FIG. 11 and recombination of dangling bonds. Also, C₁₁₆shown in FIG. 13 is obtained by desorption of two carbon atoms of theladder-like cross-linking of C₁₁₈ of FIG. 12 and recombination of bonds.Judging from the fact that there are scarcely observed odd-numberedclusters in the dimeric TOF-MS, and from the structural stability, itmay be presumed that the loss in C₂ is not produced directly from1,2-(C₆₀)2, but rather that it is produced through C₁₂₀ (d) of FIG. 11.

Also, Osawa et al states in the above-mentioned literature that D5dsymmetrical C₁₂₀ structure is obtained from C₁₂₀ (a) through structurerelaxation by multi-stage Stone-Wales transition. However, insofar asthe TOF-MS of the C₆₀ polymer is concerned, it is not the structurerelaxation by the multi-stage transition reaction but rather the processof structure relaxation accompanied by C₂ loss that governs theformation of the polymer by plasma irradiation.

In a planar covalent compound in general, in which a π-orbital crossesthe σ-orbital, spin transition between 1(π−π*)−3(π−π*) is a taboo, whileit is allowed if, by vibration-electric interaction, there is mixed theσ-orbital. In the case of C₆₀, since the π-orbital is mixed with theσ-orbital due to non-planarity of the π covalent system, inter-statecrossing by spin-orbital interaction between 1(π−π*) and 3(π−π*) becomespossible, thus producing the high photochemical reactivity of C₆₀.

The plasma polymerization method is applicable to polymerization of C₇₀molecules. However, the polymerization between C₇₀ molecules is moredifficult to understand than in that between C₆₀. Thus, thepolymerization is hereinafter explained in as plain terms as possiblewith the aid of numbering of carbon atoms making up C₇₀ as shown in FIG.14.

The 105 C—C bonds of C₇₀ are classified into eight sorts of bondsrepresented by C(1)-C(2), C(2)-C(4), C(4)-C(5), C(5)-C(6), C(5)-C(10),C(9)-C(10), C(10)-C(11) and C(11)-C(12). Of these, C(2)-C(4) andC(5)-C(6) are of the same order of double bond performance as the C═C inC₆₀. The π-electrons of the six members of this molecule including C(9),C(10), C(11), C(14) and C(15) are non-localized such that the C(9)-C(10)of the five-membered ring exhibit the performance of the double bond,while the C(11)-C(12) bond exhibits single bond performance. Thepolymerization of C₇₀ is scrutinized as to C(2)-C(4), C(5)-C(6),C(9)-C(10) and C(10)-C(11) exhibiting the double-bond performance.Meanwhile, although the C(11)-C(12) is substantially a single bond, itis a bond across two six-membered rings (6,6-ring fusion). Therefore,the addition reaction performance of this bond is also scrutinized.

First, the [2+2] cycloaddition reaction of C₇₀ is scrutinized. From the[2+2] cycloaddition reaction of these five sorts of the C—C bonds, 25sorts of dimers of C₇₀ are produced. For convenience of calculations,only nine sorts of the addition reactions between the same C—C bonds arescrutinized. Table 1 shows heat of the reaction (ΔHf0(r)) in the courseof the process of yielding C₁₄₀ from C₇₀ of two molecules of theMNDO/AN-1 and PM-3 levels.

TABLE 1 ΔHf0(r) (kcal.mol) cluster (reference ACTUATING ΔHf0(r)(kcal/mol) drawing) MEANS-1 PM-3 cross-linking bond length (Å) C140(a)−34.63 −38.01 C(2)-C(2′), C(4)-C(4′) 1544 (FIG. 15) C(2)-C(4),C(2)-C(4′) 1607 C140(b) −34.33 −38.00 C(2)-C(4′), C(4)-C(2′) 1544 (FIG.16) C(2)-C(4), C(2′)-C(4′) 1607 C140(c) −33.94 −38.12 C(5)-C(5′),C(6)-C(6′) 1550 (FIG. 17) C(5)-C(6), C(5′)-C(6′) 1613 C140(d) −33.92−38.08 C(5)-C(6′), C(6)-C(5′) 1551 (FIG. 18) C(5)-C(6), C(5′)-C(6′) 1624C140(e) −19.05 −20.28 C(9)-C(9′), C(10)-C(10′) 1553 (FIG. 19)C(9)-C(10), C(9′)-C(10′) 1655 C140(f) −18.54 −19.72 C(9)-C(10′),C(10)-C(9′) 1555 (FIG. 20) C(9)-C(10), C(9′)-C(10′) 1655 C140(g) +3.19−3.72 C(10)-C(10′), C(11)-C(11′) 1559 (FIG. 21) C(10)-C(11),C(10′)-C(11′) 1613 C140(h) +3.27 −3.23 C(10)-C(11′), C(11)-C(10′) 1560(FIG. 22) C(10)-C(11), C(10′)-C(11′) 1613 C140(i) +64.30 +56.38C(11)-C(11′), C(12)-C(12′) 1560 (FIG. 23) C(11)-C(12), C(11)-C(12′) 1683

In the table, ΔHf0(r)ACTUATING MEANS-1 and ΔHf° (r)PM-3 means calculatedvalues of the heat of reaction in case of using parameterization of theMNDO method which is a semi-empirical molecular starting method by J. J.Stewart.

In the above Table, C₁₄₀ (a) and (b), C₁₄₀ (c) and (d), C₁₄₀ (e) and (f)and C₁₄₀ (g) and (h) are anti-syn isomer pairs of the C2)-C(4),C(5)-C(6), C(9)-C(10) and C(10)-C(11) bonds, respectively. In theaddition reaction between C(11) and C(12), only D2h symmetrical C₁₄₀ (i)is obtained. These structures are shown in FIGS. 15 to 23. Meanwhile, aninitial structure of a C₇₀ polymer by the most stable [2+2]cycloaddition is shown in FIG. 24.

The utmost stability of the [2+2] cyclic additive structure indicates,in other words, that the C(2)-C(4) bond of the C70 molecular model ishighest in addition reactivity.

From this Table 1, no energy difference is seen to exist between theanti-syn isomers. The addition reaction between the C(2)-C(4) andC(5)-C(6) bonds is as exothermic as the addition reaction of C60,whereas that between the C(11)-C(12) is appreciably endothermic.Meanwhile, the C(1)-C(2) bond is evidently a single bond. The heat ofreaction of the cycloaddition reaction in this bond is +0.19 and −1.88kcal/mol at the ACTUATING MEANS-1 and PM-3 level, respectively, whichare approximately equal to the heat of reaction in C₁₄₀ (g) and (h).This suggests that the cycloaddition reaction across the C(10) and C(11)cannot occur thermodynamically. Therefore, the addition polymerizationreaction across the C₇₀ molecules occurs predominantly across theC(2)-C(4) and C(5)-C(6), whereas the polymerization across theC(9)-C(10) bonds is only of low probability, if such polymerizationtakes place. It may be premeditated that the heat of reaction across theC(11)-C(12), exhibiting single-bond performance, becomes larger thanthat across the bond C(1)-C(2) due to the appreciably large pinch of thecyclobutane structure of C₁₄₀ (i), in particular the C(11)-C(12) bond.For evaluating the effect of superposition of the 2p2 lobe of sp2 carbonneighboring to the cross-linking bondage at the time of [2+2]cycloaddition, the values of heat generated in the C₇₀ dimer, C₇₀-C₆₀polymer and C₇₀H₂ were compared. Although detailed numerical data arenot shown, it may be premeditated that the effect of superposition canbe safely disregarded across C₁₄₀ (a) to (h), insofar as calculations ofthe MNDO approximate level are concerned.

The mass distribution in the vicinity of the dimer by the LDITOF-MS ofthe C₇₀ polymer film indicates that dimers of C₁₁₆, C₁₁₈ etc are mainproducts. Then, scrutiny is made into the structure of C₁₃₆ produced ondesorbing four carbon atoms making up cyclobutane of a dimer (C₇₀)2, asin the process of obtaining D2h-symmetrical C₁₁₆ from C₆₀ andrecombining remaining C₆₈. These structures are shown in FIGS. 28 to 36.Table 2 shows comparative values of the generated heat (ΔHf0) of C₁₃₆.

TABLE 2 cluster (reference ΔHf0(r) (kcal/mol) ΔHf0(r) (kcal/mol)drawing) AN-1 PM-3 cross-linking bond length (Å) C136(a) −65.50 −61.60C(1)-C(8′), C(3)-C(5′) 1.351 (FIG. 24) C(5)-C(3′), C(8)-C(1′) 1.351C136(b) −64.44 −61.54 C(1)-C(3′), C(3)-C(1′) 1.351 (FIG. 25) C(5)-C(8′),C(8)-C(5′) 1.351 C136(c) 0 0 C(4)-C(13′), C(7)-C(10′) 1.352 (FIG. 26)C(10)-C(7′), C(13)-C(4′) 1.352 C136(d) +0.09 +0.11 C(4)-C(7′),C(7)-C(4′) 1.351 (FIG. 27) C(10)-C(13′), C(13)-C(10′) 1.354 C136(e)+112.98 +102.89 C(5)-C(8′), C(8)-C(5′) 1.353 (FIG. 28) C(11)-C(14′),C(14)-C(11′) 1.372 C136(f) +69.47 +59.44 C(5)-C(14′), C(14)-C(5′) 1.358(FIG. 29) C(11)-C(8′), C(8)-C(11′) 1.352 C136(g) −3.74 −9.20C(5)-C(15′), C(15)-C(5′) 1.344 (FIG. 30) C(12)-C(9′), C(9)-C(12′) 1.352C136(h) +2.82 −5.30 C(5)-C(9′), C(9)-C(5′) 1.372 (FIG. 31) C(12)-C(15′),C(15)-C(12′) 1.334 C136(i) +98.50 +84.36 C(13)-C(10′), C(15)-C(16′)1.376 (FIG. 32) C(10)-C(13′), C(16)-C(15′) 1.376

In Table 2, ΔHf0 ACTUATING MEANS-1, ΔHf0 PM-3, cross-linking and thebinding length are the same as those of Table 1.

52.

It is noted that C₁₃₆ (a) to (i) are associated with C₁₄₀ (a) to (i),such that C(2) and C(4), which formed a cross-link at C₁₄₀(a), have beendesorbed at C₁₃₆(a). It is noted that carbon atoms taking part in thefour cross-links of C₁₃₆(a) are C(1), C(3), C(5) and C(8), these beingSP2 carbon atoms. Among the dimers shown in Table 1, that estimated tobe of the most stable structure at the PM-3 level is C₁₄₀(c). Therefore,in Table 2, ΔHf0 of C₁₃₆(c), obtained from C₁₄₀(c), is set as thereference for comparison. It may be seen from Table 2 that thestructures of C₁₃₆(a) and C₁₃₆(b) are appreciably stabilized and thatC₁₃₆(e), C₁₃₆(f) and C₁₃₆(i) are unstable. If the calculated values ofΔHf0 of per a unit carbon atom of the totality of C₁₄₀ and C₁₃₆structures are evaluated, structure relaxation in the process from C₁₄₀to C₁₃₆ only take place in the process from C₁₄₀(a) and (b) to C₁₃₆(a)and (b). Thus, the calculations of the MNDO approximation level suggestthat, in the C₇₀ cross-link, not only are the sites of the [2+2]cycloaddition of the initial process limited to the vicinity of both endfive-membered rings traversed by the main molecular axis, but also isthe cross-link structure of the π-covalent system, such as C₁₃₆, limitedto C₁₃₆ obtained from the dimer of C₇₀ by the cycloaddition reactionacross C(2)-C(4) bond. The molecular structure of more stable C136,yielded in the process of relaxation of the structure shown in FIG. 24,is shown in FIG. 34.

The polymer film of C60 shows semi-conductivity with the band gapevaluated from temperature dependency of the dark current being of theorder of 1.5 to 2 eV. The dark conducivity of the C₆₀ polymer filmobtained with the micro-wave power of 200 W is on the order of 10⁻⁷ to10⁻⁸ S/cm, whereas that of the C₇₀ polymer film obtained for the samemicro-wave power is not higher than 10⁻¹³ S/cm, which is approximate toa value of an insulator. This difference in the electrical conductivityof the polymer films is possibly attributable to the structures of thepolymer films. Similarly to the sole cross-link bond in whichtwo-molecular C₆₀ is in the state of open-shell radical state, thecross-link of a dimer of 1,2-C(60) due to [2+2] cycloaddition reactionof FIG. 8 is thought not to contribute to improved electricallyconductivity. Conversely, the inter-molecular cross-link, such as C₁₁₆,forms the π-covalent system, and hence is felt to contribute to improvedelectrically conductivity. The cross-link structures of C₁₁₈, C₁₁₄ andC₁₁₂, now under investigations, are thought to be a π-covalentcross-link contributing to electrically conductivity.

It may be contemplated that the electrical conductivity usually is notincreased linearly relative to the number of electrically conductivecross-links between fullerene molecules, but is changed significantlybeyond the permeation limit at a certain fixed number. In the case ofC₇₀, the probability of the [2+2] cycloaddition reaction is presumablylower than that in the case of C₆₀, while the structure relaxation tothe electrically conductive cross-linked structure such as that fromC₁₄₀ to C₁₃₆ can occur only on specified sites. In light of the above,the significant difference in electrically conductivity between the twomay possibly be attributable to the fact that, in the C₆₀ polymer film,the number of cross-links contributing to electrically conductivity islarge and exceeds the permeation limit, whereas, in the case of C₇₀, thepermeation limit is not exceeded because of the low probability ofpolymerization and limitation of formation of electrically conductivecross-links.

In the foregoing, explanation has been made on the discovery offullerene molecules, fullerene vapor-deposited film, fullerene polymerfilm and the polymerization mechanism. The manufacturing method for thefullerene molecules, the film-forming method for the fullerenevapor-deposited film and the fullerene polymer film by polymerizationwill hereinafter be explained with reference to the drawings.

First, the fullerene molecules, as a starting material, those of C₆₀,C₇₀ and higher-order fullerene may be used, either singly or incombination. Most preferred are the C₆₀ fullerene, the C₇₀ fullerene ormixtures thereof. In addition, the fullerene of higher orders, such asC₇₀, C₇₈, C₈₀, C₈₂, C₈₄ and so forth may be contained therein.

These fullerene molecules may be manufactured by an arc discharge methodof a carbon electrode, using an apparatus shown for example in FIG. 35.

In a reaction vessel 8 of the present apparatus, there are mounted apair of carbon electrodes, connected to an AC or DC source 9, such ascounter-electrodes 10 a, 10 b formed of graphite. After evacuating thereaction vessel 8 by a vacuum pump through an exhaust pump, low-pressureinert gas, such as helium or argon, is introduced via an inlet 11 a soas to be charged into the reaction vessel 8.

The ends of the counter-electrodes 10 a, 10 b are arranged facing eachother with a small gap in-between, and a predetermined current andvoltage are applied from the DC source 9 to maintain the state of arcdischarge across the ends of the counter-electrodes 10 a, 10 b for apredetermined time.

By this arc discharge, the counter-electrodes 10 a, 10 b are vaporizedso that soot is gradually deposited on a substrate 12 mounted on theinner wall surface of the reaction vessel 8. If this amount of sootdeposited is increased, the reaction vessel 8 is cooled and thesubstrate 12 is taken out, or the soot is recovered using a sweeper.

This soot contains various fullerene molecules, including C₆₀ and C₇₀,and may contain approximately not less than 10% of fullerene molecules,depending on circumstances.

From this soot, the fullerene such as C₆₀ or C₇₀ may be extracted usingsolvent, such as toluene, benzene or carbon disulfide. The yieldedfullerene, obtained in this stage, is termed crude fullerene, which maybe applied to column chromatography to separate C₆₀ and C₇₀ as purifiedseparate products.

The resulting fullerene molecules are used as a starting material in thefilm-forming process of the fullerene polymer. Among the polymerizationor film-forming methods, there are, for example, an electron beamillumination method, an electromagnetic polymerization method,photopolymerization method, plasma polymerization method, micro-wavepolymerization method and an electronic polymerization method.

Fullerene Vapor-Deposition Method

For this vapor deposition, a vapor-deposition device comprising areaction chamber capable of maintaining vacuum or lower pressure, andheating means provided therein for vaporizing fullerene molecules, suchas resistance beating. The fullerene molecules are vaporized on heatingto form a vapor-deposited film on a substrate carrying theabove-mentioned carbonaceous thin film.

Photopolymerization Method

In this polymerization method, an apparatus including a reaction chambercapable of being maintained at a reduced pressure or in vacuum, heatingmeans, such as resistance heating means, for vaporizing the fullerenemolecules, and illumination means for illuminating the light, such asultraviolet beam, through the window of the reaction chamber, is used. Afullerene polymer film is formed on the substrate as fullerene isevaporated and illumination of ultraviolet light is continued for apredetermined time. At this time, the fullerene molecules are excited bylight and polymerized through the excited state.

It is noted that polymerization occurs by forming an evaporated film andilluminating ultraviolet rays thereon, without illuminating the light asthe evaporation is going on. In this case, there are occasions whereinonly a superficial layer of the film is polymerized, whilst the insideof the film is not polymerized. An experiment conducted by the presentinventors have revealed that a pattern of cracks can be produced on thesurface of the evaporated fullerene film on UV irradiation, as may beobserved over a microscope.

Electron Beam Polymerization Method

This method uses an electron beam radiated from the electron gun inplace of the light such as ultraviolet light. The principle ofpolymerization is similar to the photo polymerization method, that is,the fullerene molecules are excited by an electron beam and polymerizedthrough the excited state.

X-Ray Polymerization Method

This method uses X-rays radiated from an X-ray tube in place of anelectron beam. The principle of polymerization is the same as that ofthe electron beam. The fullerene molecules are excited by X-rays andpolymerized through this excited state.

Plasma Polymerization Method

Among the plasma polymerization methods, there are a high-frequencyplasma method, a DC plasma method and an ECR plasma method. Here, thehigh-frequency plasma method, which is now in widespread use, isexplained by referring to the drawings.

FIG. 36 shows a typical high-frequency plasma polymerization apparatus,including a vacuum vessel 13, within which are arranged a pair ofelectrodes 14 a, 14 b facing each other. These electrodes are connectedto an outer high frequency power source 15. On one 14 b of theelectrodes is set a substrate 16 for permitting a fullerene polymer filmto be deposited thereon.

In this vacuum vessel 13, there is arranged a vessel 17 formed e.g., bya molybdenum boat, accommodating the fullerene molecules, as a startingmaterial. This vessel 17 is connected to an external power source forresistance heating 18.

In the polymerization apparatus, constructed as described above, alow-pressure inert gas, such as argon, is introduced through an inlet 19into the vacuum vessel 13, which is evacuated through the exhaust port20. After the vacuum vessel 13 is charged with the inert gas, thecurrent is supplied to the vessel 17 to heat it to vaporize thefullerene molecules therein. The high frequency voltage is applied fromthe high frequency power source 15 to generate a high frequency plasmaacross the electrodes, while illumination is made into the fullerene gasto form a fullerene polymer film holding the π-electron skeleton on thesubstrate 16.

Meanwhile, a DC power source may be used in place of the high frequencypower source 15 (DC plasma method). If the vessel 17 is heated withoutactuating these power sources, that is without generating the plasma,the fullerene is not polymerized, but its evaporated film is formed onthe substrate 16.

If the temperature of the substrate 16 is excessively high, the amountof deposition of the fullerene polymer film is decreased. Therefore, thesubstrate is usually kept at a temperature of 300° C. or less. If theplasma power is of the order of 100 W, the temperature scarcely exceeds70° C.

Method of Illuminating the Evaporated Film with Electromagnetic Wave

This technique furnishes a method for generating a fullerene polymer byvacuum depositing fullerene molecules and then illuminatingelectromagnetic waves such as RF plasma thereon to polymerize thefullerene molecules , and a manufacturing method for a functionalelement employing the fullerene polymer film as a functional elementconstituting layer.

In the fullerene molecules, functional element, and manufacturing methodtherefor, a vapor-deposited film of fullerene molecules is first formedand polymerized on illumination of electromagnetic waves, so that, byfirst measuring the thickness of the vapor-deposited film and bycontrolling the vapor deposition conditions, such as vapor depositiontemperature, a vapor-deposited film of a desired film thickness canperpetually be produced. Thus, the film thickness of the fullerenepolymer film by illumination of electromagnetic waves can be easily andeffectively controlled to achieve a desired film thickness.

Moreover, since the fullerene vapor-deposited film is polymerized as thestructure of the fullerene molecules constituting the vapor-depositedfilm is kept, so that a fullerene polymer film of a neat structure withthe fullerene molecule skeleton can be formed. Should an organic filmetc be present in the underlying layer, the vapor-deposited film formedthereon does not damage the underlying layer, which may also beprotected from radiation of electromagnetic waves due to the presence ofthe vapor-deposited film.

In the present technique, a vapor-deposited film 4A of fullerenemolecules, such as C₆₀, is formed on a substrate 16, as shown in FIG.37A. During evaporation, the film thickness of the vapor-deposited film4A is measured to control the film thickness to e.g., 10 Å (thickness ofa single molecular layer) to 200 nm. After forming the vapor-depositedfilm of a desired thickness, the vapor-deposited film 4A is polymerizedby illumination of electromagnetic waves 10, such as RF plasma, topolymerize the vapor-deposited film 4A to form the fullerene polymerfilm 4A, as shown in FIG. 37B. The film thickness is measured using afilm thickness meter 11 arranged in the vacuum chamber 13, as shown inFIG. 38.

FIG. 38 shows an evaporation device including a susceptor 12 arranged inthe vacuum vessel 13. On the susceptor 12 is set a substrate on which todeposit an evaporated fullerene film. This substrate may, for example,be a substrate 1 on which an electrically conductive high molecular filmhas been formed on a light-transmitting electrode.

In the vacuum vessel 13 is arranged a vessel 17, such as a molybdenumboat, for accommodating fullerene molecules as a starting materialtherein. This vessel is connected to an external resistance heatingpower source 18.

In the evaporation device, constructed as described above, the currentis supplied to the vessel 17 in the evacuated vacuum vessel 13, to heatthe vessel to vaporize the fullerene molecules therein to form anevaporated fullerene film of fullerene 4A on the substrate 1.

Then, in a high frequency plasma polymerization apparatus of FIG. 39, inwhich a pair of electrodes 14 a, 14 b are arranged facing each other ina vacuum vessel 23 and are connected to ah external high frequency powersource 15, the substrate 1, carrying the evaporated fullerene film 4A,is set.

In this polymerization apparatus, a low pressure inert gas, such asargon, is supplied into the vacuum vessel 23, evacuated through theexhaust port 20, to fill the inside of the vacuum vessel 23 with thegas. The high frequency voltage is applied from the high frequency powersource 15 to generate a high frequency plasma across the electrodes 14 aand 14 b, at the same time as the evaporated fullerene film 4A isilluminated and thereby polymerized to form a fullerene polymer film 4having the π-electronic skeleton.

The high frequency power source 15 may be replaced by a DC power source(direct current plasma method). If the devices of FIGS. 38 and 39 arecombined as shown in FIG. 36, and the vessel 17 is heated withoutdriving the power source 15, that is without generating the plasma, theevaporated fullerene film 4A is formed on the substrate 1. The powersource 15 may be driven in the same apparatus to effect polymerizationin a manner as described above.

The fullerene molecules may be fullerenes C₆₀ or C₇₀ by itself or amixture thereof. The electromagnetic waves illuminated may be RF plasma,UV rays or electron rays.

Microwave Polymerization Method

FIG. 40 shows a typical microwave polymerization apparatus including avessel 21, such as a molybdenum boat, accommodating the fullerenemolecules as a supply source of a starting material, a microwaveoperating portion 23 for causing the microwave 22 to operate on flyingfullerene molecules, a reaction chamber 25 for generating a fullerenepolymer by induction by the microwave 22 (excitation of asymmetricplasma) and for forming its film on the gas 24, and a microwavegenerating device for generating the microwave 22.

In an inner wall of the polymerization apparatus in the vicinity of thevessel 21 is opened a gas inlet tube 26 for introducing a carrier gas,such as an argon gas, into the inside of the apparatus. This carrier gas27 has not only the capability of entraining fullerene molecules 27 tobring them onto the substrate 24 in the reaction chamber 25 but thecapability of modifying the surface of the substrate 24 in the followingmanner.

That is, if, before introducing the fullerene molecules 28 into theinside of the apparatus, the carrier gas 27 is introduced and excited bythe microwave operating portion 23 so as to be bombarded onto thesurface of the substrate 24 in the reaction chamber 25, the substratesurface is etched by the excited carrier gas 27 to improve adhesion ofthe substrate surface with the fullerene polymer film deposited thereon.

The microwave generating device (microwave unit) includes a microwaveoscillation source 29, an isolator 30, a power meter 31, a microwavepower tuner 32 and a reflection cavity 34, interconnected by a waveguide tube 35. Of these, the microwave oscillation source 29 is made upof an oscillation source, such as a magnetron, whilst the isolator 30and the power meter 31 have the functions of rectifying the microwaveand of detecting the microwave power. The microwave power tuner 32 is adevice for adjusting the number of oscillations of the microwave, havingthe function of matching the number of oscillations, whilst thereflection cavity 34 is a device for reflecting the microwave andmatching the wavelength to convert the microwave in the microwaveoperating portion 23 into a standing wave.

The reaction chamber 25 may be larger in diameter than a resonant tube36 which is a flow duct of the carrier gas 27 and the fullerenemolecules 28, and is configured so that the fullerene molecules inducedefficiently to high density in the microwave operating portion 23 of theresonant tube will be led onto a substrate 24 of e.g., silicon, providedon a support, not shown, where the fullerene polymer film will be formeduniformly. In the reaction chamber 25, there is provided an evacuatingsystem 37 for maintaining a pre-set pressure in the reaction chamber 25.

The support for mounting the substrate 24 thereon may be electricallyconductive or insulating. It may also be provided with heating means,such as current supplying means.

If this microwave polymerization device is to be used, the inside of thereaction chamber 25 is maintained at a pressure of approximately 0.05 to1 Torr, with e.g., an argon gas, whilst the vessel 21 is heated byheating means, not shown, for vaporizing the fullerene moleculestherein. The vaporized fullerene molecules then are illuminated withe.g., a high frequency plasma of the order of 13.56 MHz by the microwaveoperating portion 23. This excites the fullerene molecules to form afullerene polymer film on the substrate 24.

The temperature of the substrate 24 of 300° C. or less usually suffices.If this temperature exceeds 300° C., the amount of deposition of thefullerene polymer film is occasionally lowered. It is noted however thatdeposition of the fullerene polymer film is facilitated by applying abias voltage. No special control is needed to maintain the substratetemperature in the above range during film formation. For example, ifthe microwave power is of the order of 100 W, the temperature rarelyexceeds 100° C. Meanwhile, if the substrate 24 is put on the microwaveoperating portion 23, the tel is occasionally increased to near 1000° C.

Electrolytic Polymerization Method

FIG. 41 shows a typical electrolytic polymerization apparatus in whichan electrode 39 as a positive electrode and an electrode 40 as anegative electrode, both connected to a potentiostat 41, are provided inan electrolytic cell 38, and in which a reference electrode 42 isconnected to the same potentiostat 41 so that a pre-set electricpotential is applied across the electrodes 39 and 40.

The electrolytic cell 38 is provided with a gas inlet tube 45 forintroducing the inert gas 44 for removing an oxygen gas etc from anon-aqueous solvent 43. In a lower portion of the electrolytic cell 38,there is provided a magnetic stirrer 46 for causing movement of astirrer, not shown, provided in the cell.

For operating the electrolytic polymerization apparatus, constructed asdescribed above, fullerene molecules, as starting material, a supportingelectrolyte, for accelerating electrolysis, and the non-aqueous solvent43, are charged into the electrolytic cell 38 and the potentiostat 41 isoperated to cause a pre-set electrical energy to operate across theelectrodes 39, 40. Then, a majority of the fullerene molecules areturned into anionic radicals, whilst a fullerene polymer is formed as aprecipitate as a thin film and/or a precipitate on the negativeelectrode 40. Meanwhile, the spherically-shaped fullerene polymer,obtained as a precipitate, can be readily recovered by filtration ordrying. After recovery, the polymer can be solidified or kneaded into aresin to form a thin film.

Although the electrodes 39, 40 are preferably metal electrodes, they mayalso be formed of other electrically conductive materials, or by vapordepositing metal or other electrically conductive materials on a siliconor glass substrate. The materials of the reference electrode 42 need notbe limited to particular metals, depending on the sort of the supportingelectrolyte.

The removal of e.g., oxygen by the inert gas 44 may usually be heliumgas bubbling. The helium gas may also be replaced by other inert gases,such as nitrogen or argon. For completely removing oxygen etc, it isadvisable to dehydrate the non-aqueous solvent, composed of first andsecond solvents, as later explained, using a dehydrating agent, toevacuate the solvent, to save the respective solvents in ampoules and tointroduce the solvents saved in the ampoules through a vacuum line intothe electrolytic cell 38.

It should be noted that oxygen etc is removed from the electrolyticsolution in order to prevent oxygen etc from being captured into thefullerene polymer film to suppress paramagnetic centers to improvestability of the fullerene polymer film.

As the supporting electrolyte, tetrabutyl ammonium perchloride, lithiumtetrafluoro borate (LiBF₄), lithium hexafluoro phosphate (LiPF₆), sodiumperoxide (NaClO₄), LiCF₃SO₃, and lithium hexafluoro arsenide (LiAsF₆)may be used. If these supporting electrolytes are used, the producedspherical carbon polymers tend to be precipitated in the electrolyticsolution.

If lithium perchloride (LiClO₄) or tert-butyl ammonium perchlorate isused, a spherically-shaped carbon polymer can be produced as a thin filmon the electrode.

There are occasions wherein the physical properties of the fullerenepolymer film produced on the electrode are slightly affected dependingon selection of the supporting electrolytes. In general, if largepositive ions, such as ammonium salts, are present as counter-ions in anon-aqueous solvent, a fullerene polymer film of lower mechanicalstrength tends to be deposited on the electrode. On the other hand, iflithium ions are present as counter-ions, there is produced a fullerenepolymer film having a larger mechanical strength and a mirror-likesurface.

According to the present invention, a mixed solvent composed of a firstsolvent, capable of dissolving fullerene molecules, and a secondsolvent, capable of dissolving the supporting electrolyte, is preferablyemployed. The mixing ratio of the first solvent to the second solvent ispreferably 1:10 to 10:1 in volume ratio.

The first solvent is preferably a solvent of lower polarity, having aπ-electrolytic system (low polarity solvent). Examples of this sort ofthe solvent include one or more selected from the group of carbondisulfide (CS₂), toluene, benzene and o-dichlorobenzene.

The second solvent is preferably an organic solvent having a highdielectric constant, such as, for example, acetonitrile, dimethylformamide, dimethyl sulfoxide and dimethyl acetoamide. Of these,acetonitrile is most preferred.

In general, the fullerene molecules are dissolved only in low-polarsolvent, such as carbon disulfide, while being extremely low insolubility even in aliphatic solvents. such as n-hexane. This is themost serious problem in electrolytic polymerization of the fullerenemolecules.

The reason is that the supporting electrolyte used in electrolyticpolymerization is dissolved only in polar solvents, such as water.

In carrying out electrolytic polymerization of the fullerene molecules,it is necessary to use such a solvent as is capable of dissolving boththe fullerene molecules and the supporting electrolyte. However, therelacks a single solvent satisfying this condition. At least a mixedsolvent made up of individual solvents having the above-mentioneddissolving properties needs to be used.

However, mixed solvents satisfying these conditions may notunconditionally be used. If such mixed solvent simply is used, it is afrequent occurrence that the solvent is insufficient in solubility forthe fullerene molecules and/or the supporting electrolyte.

For example, an aqueous solvent, including water, is known to be anoptimum solvent for the supporting electrolyte which is a salt. However,it is only insufficiently soluble in the low-polar solvent capable ofdissolving fullerene molecules. Therefore, the mixed solvent composed ofthe two solvents cannot be said to be optimum.

Our researches have revealed that the desirable mixed solvent used inthe present invention is made up of the first and second solvents, withthe first solvent being a low polar solvent and the second solvent beingan organic solvent of high polarity and large dielectric constant.

Among the above-specified second solvents, acetonitrile, a solventfrequently used in preparing radicals of an organic matter in thepresence of a supporting electrolyte in an electrolytic cell, is mostpreferred.

It is however unnecessary to use this acetonitrile as the second solventsince dimethyl formamide or other organic solvents are also desirablyused in the present invention.

In applying the potential during electrolytic polymerization, one of theconstant current mode and the constant voltage mode may be selectivelyused. In the former mode, if a high-resistance fullerene polymer film isformed on an electrode, the current value tends to be lowered to raisethe voltage. In such situation, it is difficult to maintain a constantreaction because of different states of fullerene polyanions. It istherefore preferred to carry out electrolytic polymerization under theconstant voltage mode, even if the current value is undesirably lowered.

If electrolytic polymerization is effected simply under a constantpotential condition, it is unnecessary to limit the power source only tothe potentiostat, shown in the drawing, such that it suffices to use asimple DC power source comprised of a dry cell and a variable resistorboth of which are commercially available.

Using an apparatus shown in FIG. 41, fullerene polymerization waseffected in the presence of a variety of supporting electrolytes. Ouranalyses have indicated that the fullerene molecules, if dissolved, areturned into electrically negative anion radicals. Since these anionradicals are reacted with electrically neutral fullerene molecules orwith one another, so that a fullerene polymer film is produced on theelectrode. This polymerization process is in need of extremely delicatetemperature control and control of the electrolytic potential. If theaforementioned specified mixed solvent is used, it is not so hard todissolve the fullerene molecules or to donate electrical charges.However, if polymerization has occurred not on the electrode surface butin the mixed solvent, the fullerene polymer is precipitated because ofthe low solubility. If the amount of the precipitate is excessive, it isnot deposited efficiently on the electrode surface to lower theefficiency in thin film formation. If, in general, heating foraccelerating the reaction is not performed and lithium is reacted aspositive ions of the supporting electrolyte, there is produced a solidlustrous fullerene polymer film.

The above-described electrolytic polymerization method for fullerene hasinherently developed by the present inventor in order to produce afullerene polymer film composed only of [2+2] cycloaddition of C60fullerene. Such polymer cannot be produced by the gas phase reaction,such as other plasma polymerization method. The present inventor hasconducted scrutiny, based on semi-empirical level molecular orbitcalculations, as to whether or not the aforementioned electrolyticpolymerization reaction is possible thermo-dynamically. If thecounter-ion is lithium, the results of calculations of MNDOapproximations, in which atomic parameters of lithium ions are set,predicted the following values of the generated heat for C₆₀, C₆₀—Li,C₁₂₀—Li and C₁₂₀—L2.

C₆₀: 869.4182 kcal/mol

C₆₀—Li: 768.001 kcal/mol

C₁₂₀—Li: 1525.716 kcal/mol

C₁₂₀—Li2: 1479.057 kcal/mol

It is noted that C₁₂₀ is a dimer of C₆₀ resulting from cyclo-addition,shown in FIG. 8, and that lithium ion has the most stable structure inwhich the lithium ion is sandwiched between two fullerene molecules ofthe cross-linked structure. The calculations of the system including thelithium compound were executed in their entirety by a non-limitingHartrey-Fock method. From these results of calculations, the flowingconclusions are derived:

(1) C₆₀ is appreciably stabilized by lithium coordination. This isascribable to the fact that the lowest void orbit of C₆₀ is at anappreciably lower position than free electrons.

(2) the heat of reaction of C₆₀+C₆₀—Li=C₁₂₀—Li is predicted to be−106.703 kcal/mol to promote stabilization.

(3) The reaction heat of 2C₆₀—Li=C₁₂₀—Li is predicted to be −46.945kcal/mol, this reaction being similarly exothermic. These results ofcalculations represent the energy difference between the initial stateand the terminal state in vacuum and are not intended to find out thepotential barrier to the reaction. However, the present results ofcalculations support the fact that, if there is only negligible entropycontribution, such as steric hindrance, during the reaction, there isobtained good correlation with the free energy of the system, such thatthe aforementioned reaction can take place easily.

On the surface of the fullerene polymer film, obtained by theabove-mentioned different polymerization methods, there are partiallyleft fullerene molecular structures, so that numerous bonds of thedouble bond type exist. Therefore, surface modification (surfaceprocessing) in a variety of ways is possible.

For example, the fullerene polymer film can be surface-modified, usingtechniques such as microwave induction, DC plasma or AC plasma, in anatmosphere of a hydrocarbon gas, such as acetylene, methane, ethane,propane, toluene, benzene, acetone, acetonitrile, ethanol or methanol,or a gas, such as oxygen, hydrogen, chlorine or fluorine. Alternatively,the fullerene polymer film may be surface-modified in a solvent usingmetal complex compounds or organic radicals.

This surface modification is effective to modify the fullerene polymerfilm or to afford specificity thereto depending on the objective orapplication.

Meanwhile, the fullerene polymer film, in particular the fullerenepolymer film obtained by the microwave polymerization method, suffersthe problem of dangling spin. If, for example, microwave polymerizationis carried out at ambient temperature with a power of from 100 W tohundreds of W, using C₆₀ and/or C₇₀ as a starting material, there isproduced a fullerene polymer film containing approximately 10¹⁸ spins/gof dangling spin.

This dangling spin significantly affects the electrically conductivityof the fullerene polymer film, band structure or chronological stabilityof the physical properties.

This dangling spin is possibly produced by the fact that no idealcross-linked structure has not been formed. The amount of the danglingspin can be reduced to some extent by adjusting the substratetemperature for depositing the fullerene polymer film or by exposing thefilm to an atmosphere such as a hydrogen plasma. The process ofdecreasing the amount of the dangling spins may be confirmed from thedifference in the absorption intensity by the electron spin resonancemethod.

By the above method, a layered assembly of a substrate—a carbonaceousthin film—a fullerene thin film, essential to the present invention, isprepared. According to the present invention, this layered assembly canbe further processed depending on the objective or the intended usage.For example, a light transmitting electrode may be deposited on thefullerene thin film for usage as a solar cell, whilst a comb-shapedelectrode may be deposited for usage as a sensor.

The present invention will be explained more specifically, withreference to the drawings. However, the present invention is not limitedto these specified Examples.

EXAMPLE 1

For forming a carbonaceous thin film, a film-forming device, shown inFIG. 42, was prepared. This film-forming device is made up of a simpletype organic solvent gas bubbler 50, a gas bomb 51 for supplying thecarrier gas thereto and a simple type electrical furnace 52 forthermally decomposing the organic solvent gas. In a flow duct betweenthe gas bomb 51 and an organic solvent gas bubbler 50 and a flow ductbetween the gas bomb 51 and the electrical furnace 52, there areprovided flow adjustment needle valves 53.

The electrical furnace 52 has a core 30 mm in diameter and a quartz tube52 b is inserted into an electrical heater 52 a. Within the quartz tube52 b are set a thermocouple 52 d for connecting to an external heatertemperature controller 52 c and a quartz (glass) substrate 52 e mounteddirectly thereabove to monitor the film-forming temperature of thequartz substrate 50 e accurately. The temperature control of a quartzsubstrate 50 e is performed in cooperation with a PID control relaycircuit. The film-forming device, constructed as described above, isable to form a carbonaceous thin film within a temperature error notlarger than 1°.

The temperature in the electrical furnace 52 was set to 800° C. and,after inserting the quartz substrate 50 e into the quartz tube 52 b, anargon gas was introduced from the gas bomb 51 into the quartz tube 52 bto fill the tube with the argon gas. The argon gas was of the purity of99.999%.

When the interior of the quartz tube 52 b is completely the argon gasatmosphere and the temperature reaches 800° C., a toluene gas started tobe introduced into the interior of the quartz tube 52 b through theorganic solvent gas bubbler 50. The argon gas introduced into theorganic solvent gas bubbler 50 was set to a flow rate of 50 ml/min.

After toluene bubbling for 30 minutes, only the argon gas was againintroduced into the quartz tube 52 b to gradually cool the electricalfurnace 52. After confirming that the electrical furnace 52 was cooledto substantially the room temperature, the quartz substrate 50 e wastaken out of the quartz tube 52 b. On the surface of the quartzsubstrate 50 e was formed a carbonaceous thin film presenting a mirrorsurface.

EXAMPLE 2

Film forming as in Example 1 was carried out on a silicon substrate. Twosilicon substrates, one of which has been ground, with the othersubstrate not being ground. After cooling the electrical furnace, thetwo silicon substrates were taken out. It was found that, on the groundsilicon substrate, a carbonaceous thin film presenting a mirror surfacecomparable to that of silicon was formed, with the color of thecarbonaceous thin film being similar to the silicon substrate, whereas,on the unground silicon substrate, a black carbonaceous thin film, whichwas extremely brittle, was formed.

It is seen from this that adhesion or film-forming properties of thecarbonaceous thin film depend appreciably on the roughness of thesubstrate surface. The hardness of the carbonaceous thin films, preparedin Examples 1 and 2, was measured, with the tested film of Example 2being the carbonaceous thin film on the ground substrate. It was foundthat the carbonaceous thin film on the substrate in each of Examples 1and 2 was of a Vickers hardness of 520 to 540, thus indicating that thecarbonaceous thin film formed was markedly strong carbonaceous thinfilm, although it was not no tough as the silicon crystal.

EXAMPLE 3

For clarifying the structure of the carbonaceous thin film formed on theground silicon substrate, mass spectroscopic analysis was carried out inaccordance with the Laser-Desorption-Ionization Time-of-Flight method.For measurement, a Thermoquest Vision 2000 TOF-MS monitor was used. Thelaser used for ablation was a nitrogen laser. Before measurement, asilicon substrate was cut to a size of 5 mm and set on a target of theTOF-MS monitor. For measurement, a pulse laser was directly illuminatedon the surface of the carbonaceous thin film for excitation, desorptionand ionization. Positive ions were used for measurement. FIGS. 43 to 45show the spectrum with increased laser strength. However, the laserpower in FIG. 44 is not so strong as to vary the election valence stateof carbon. As may be seen form FIG. 44, a cluster up to 20 carbon atomsis ascribable to a continuous peak of the difference corresponding to acarbon atom and mainly to a component in the valency state of sp3. InFIG. 45, a cluster up to approximately 30 carbon atoms is mainlyascribable to a component in the valency state of sp3. If the laserpower is increased further, a continuous peak with a difference of C2from 50 to approximately 150 carbon atoms is observed. This is the peakproper to the carbon having the graphitic structure of sp2. It is seenfrom these that the carbonaceous thin film has a structure of anextremely small graphite in the random sp3 carbon.

EXAMPLE 4

For further confirming the information obtained in Example 3, an X-raydiffraction of the carbonaceous thin film was measured. Meanwhile, inX-ray and Raman measurement, as later explained, a carbonaceous thinfilm of a thicker thickness was formed by the same process. RIGAKU RADIII was used, with the line source being Cu—Kα. FIG. 46 shows thediffraction diagram. The diffraction pattern in FIG. 46 is that of acarbonaceous thin film formed on the quartz glass surface. A sole broaddiffraction line was produced and was ascribed to (002) diffraction lineof graphite. The glass usually showed broad absorption line in thevicinity of this angle. So, the same measurement was conducted for thecarbonaceous thin film deposited on a silicon substrate. The results areshown in a lower part of FIG. 46, from which it is seen that a patternsubstantially the same as that depicted above was obtained. It may beseen from this that the produced carbonaceous thin film contained anextremely small graphite structure.

For further clarifying the structure of the carbonaceous thin film,Raman measurement was conducted. The results are shown in FIG. 47.Obviously, a disordered band in the vicinity of 1350 cm⁻¹ and agraphitic band in the vicinity of 1600 cm⁻¹ were observed, with thespectrum reflecting the features of the amorphous carbon fairly well.

EXAMPLE 5

As set forth above, the carbonaceous thin film, essential to the presentinvention, is formed in strong dependency upon the substrate surfaceroughness. For checking the surface smoothness of the carbonaceous thinfilm itself, formed on the smooth surface, AFM measurement was carriedout. Using Nanoscope III, measurement of the tapping mode was carriedout.

FIG. 48 shows an image of the tapping mode AFM, while FIG. 49 shows animage indicating the surface roughness of the image of FIG. 48. It isseen from this image that the substrate surface is extremely smooth,with its roughness being on the order of 1 nm at the maximum.

EXAMPLE 6

For clarifying electronic characteristics of the carbonaceous thin film,measurement was made of the photoelectron emitting spectrum to evaluatethe valance band edge level. FIG. 50 shows the produced spectrum. It isseen from this measurement that the edge level of the carbonaceous thinfilm was 4.6 eV below the vacuum level. If this thin film has metallicelectrical conductivity similar to that of graphite, the above value isthe Fermi level.

EXAMPLE 7

For clarifying that the carbonaceous thin film shows metallic electricalconductivity or behaves as a semiconductor, the electrical conductivitywas measured in a temperature range from the liquid nitrogen temperatureto ambient temperature. The results are shown in FIG. 51, from which itis seen that the electrical conductivity of the carbonaceous thin filmshowed extremely small temperature dependency. Moreover, since theelectrical conductivity is slightly improved in the high temperaturerange as contrasted to the low temperature range, the electricalconductivity was not that of metal. Moreover, as may be seen from theelectrical conductivity plotted on the ordinate, this carbonaceous thinfilm exhibited high electrical conductivity.

EXAMPLE 8

The relationship between the absorption coefficients and the electricalconductivity of the carbonaceous thin film formed on a quartz substrateis shown in FIG. 52. Although measurement of the absorption spectrumcould not be made accurately up to the end of the optical band gap, thefact that the square value of the absorption coefficients and the photonenergy on the ordinate are linear represents the features of the skindepth absorption satisfactorily.

EXAMPLE 9

Two composite substrates were obtained by forming a platinum electrodeby sputtering on a quartz substrate and a carbonaceous thin film wasdeposited thereon as in Example 1. A composite substrate, on which thecarbonaceous thin film was deposited, was set in a plasma chamber shownin FIG. 36 and, as C₆₀ charged in the molybdenum boat was vaporized byresistance heating, a fullerene polymer film was formed to a thicknessof 1000 Å. FIG. 53 shows a tapping mode AFM image of the C₆₀ plasmapolymer film on the uppermost surface. The surface roughness of this C₆₀polymer film was approximately less than 2 nm.

EXAMPLE 10

A carbonaceous thin film was formed on a composite substrate as inExample 9. On this carbonaceous thin film was then formed a fullerenepolymer film by electrolytic polymerization by the following method.

First, a platinum electrode was set as an electrode in the electrolyticpolymerization device shown in FIG. 41, by way of a preliminary test.Using LiClO₄ as a supporting electrolyte and a mixed solvent of tolueneand acetonitrile with a toluene to acetonitrile ratio of 1:4 as asolvent, fullerene molecules (C₆₀) were dissolved in this solvent.

Using this solution, the reducing potential was measured. A redoxpotential was obtained so that the potential for e.g., the firstionization and for second ionization could be determined. Then,electrolysis was carried out in the low pressure mode at the firstionization potential, as a result of which a fullerene polymer filmcould be obtained on a platinum electrode.

FTIR (Fourier transform IR spectrum) and nuclear resonance spectrum weremeasured of the fullerene polymer film. It was found that C₆₀ moleculeswere not present in their inherent structure in the fullerene polymerfilm.

The composite substrate having the above-mentioned carbonaceous thinfilm was set in the electrolytic cell of the electrolytic polymerizationdevice. Using a mixed solvent of toluene and acetonitrile with a tolueneto acetonitrile ratio of 1:1 as a solvent, a minor amount of C₆₀molecules wee dissolved on the mixed solvent to carry out theelectrolytic polymerization. As a result, a fullerene polymer film of abrownish color was formed on the carbonaceous thin film of the compositesubstrate. AFM measurement was difficult with the fullerene polymer filmwhich was flaccid.

EXAMPLE 11

A composite substrate (by platinum sputtering) fitted with acarbonaceous thin film was prepared in the same procedure as inExample 1. This composite substrate was set on a vapor depositionmaterial and C₆₀ molecules were vapor-deposited under a pressure of 10⁻⁸Torr. The fullerene vapor-deposited film, formed on the carbonaceousthin film, was found to have a roughness extremely similar to that ofthe plasma C60 polymer film shown in FIG. 53.

EXAMPLE 12

A gold electrode was formed by sputtering on a quarts substrate, onwhich a C₆₀ plasma polymer film, a C₆₀ electrolytic polymer film and C₆₀vapor-deposited film were formed in the same way as in Examples 9 to 11to measure the electron emission spectrum of these thin films.

The results are shown in FIG. 54, from which it is seen that the valenceband edge levels of these fullerene thin film could be evaluated to be5.57, 5.68 and 6.25 eV. Since the optical band gaps of these thin filmswere on the order of 1.5, 1.4 and 1.6 eV, the carbon bond prepared inExamples 9, 10 and 11 was found to exhibit the difference on the orderof 1 eV at the minimum on the valence band edge surface level.

EXAMPLE 13

A gold electrode was formed on a quartz substrate by sputtering and acarbonaceous thin film was further deposited thereon as in Example 1.The Fermi level of this carbonaceous thin film, as measured by a contactpotential method, was evaluated to be 4.6 eV.

This measurement result substantially coincides with the valence bandedge level by the photoelectron emission method shown in FIG. 50. Theband itself of this carbonaceous thin film is thought to be extremelysmall, as may be evidenced from the evaluation of the electricalconductivity. However, the features peculiar to the p-type semiconductorare evidently noticed.

On the other hand, the fullerene polymer film has electron acceptingproperties, as may be evidenced from the ultra-aromaticity proper to thethree-dimensionally closed π-electron system.

The bond structure of the carbonaceous thin film and the fullerene thinfilm, prepared in Examples 9 to 11, is a valuable structure forseparation of carriers evolved on light illumination, such that, if itis implemented in a glass substrate—ITO electrode-carbonaceous thinfilm—fullerene thin film—aluminum electrode, it is particularly suitedfor a solar cell. This structure has moderate performance, as may beseen from its I-V characteristics on light illumination.

What is at issue in this case is that the electrical conductivity of thelight transmitting electrode is lost when forming the carbonaceous thinfilm on the light transmitting electrode, such as ITO.

For evading this problem, a complex structure of a glass substrate—thingold electrode—carbonaceous thin film—fullerene polymer film—aluminumelectrode is preferred. This complex structure operates as a solar cell,as evidenced from I-V characteristics before and after lightillumination. However, in order to realize a complex structure optimumfor this application, it is necessary to scrutinize into variablefactors, such as band gap of the carbonaceous thin film, thickness ofthe fullerene thin film or Fermi surface level of the electrodematerial.

EXAMPLE 14

A gold comb electrode was further formed on a complex structure of asubstrate—carbonaceous thin film—fullerene thin film, prepared as inExample 1, to check into the function as a gas sensor.

As result, electrical conductivity was noticed to be changed clearly ,e.g., increased, against water, acetaldehyde, formaldehyde, ammonia orformic acid. This phenomenon was similarly noticed when the combelectrode was directly mounted on the carbonaceous thin film presentinga smooth surface, such that a clear distinction was observed from a casewhen a structure comprising only an electrode without provision of thecarbonaceous thin film was used as a reference.

A comb electrode was mounted on a carbonaceous thin film prepared inExample 1, and the resulting assembly was heated at 300° C. for threehours under a vacuum of 10⁻⁸ Torr and subsequently cooled to check intochanges in electrical conductivity under an argon atmosphere of 10⁻⁸Torr to 10⁻¹ Torr.

As a result, the electrical conductivity in this pressure range wasrecognized to be changed by more than five digits of magnitude, thustestifying to the function as a pressure sensor. Also, a plasma-inducedfullerene polymer film was deposited on the carbonaceous thin film to athickness of 120 Å. The structure in this case is as shown in FIG. 1C.

Even in this structure, good changes in electrical conductivity againstthe pressure could be noticed. However, a marked difference from thestructure devoid of the fullerene polymer film as described above isthat the present structure has excellent reproducibility in electricalconductivity with respect to the cycle of pressure reduction andpressure application. This may indicate that the fullerene polymer filmoperates as passive layer.

A carbonaceous thin film then was formed on a quartz substrate, as inExample 1. In this case, three carbonaceous thin films were formed, withthe substrate temperature being changed to 750° C., 800° C. and to 850°C., and the electrical conductivity of the respective sets wasevaluated.

As a result, the electrical conductivity was improved by a factor ofthree for each of these sets. Specifically, the degree of graphizationdiffers with rise in temperature, such that graphite contribution isseen to be larger at higher temperature, as a generally well-knownphenomenon.

EXAMPLE 15

Using a film-forming device, shown in FIG. 56, a carbonaceous thin filmwas formed on a quartz substrate, by the following procedure:

Specifically, the organic solvent gas bubbler 50 was omitted from thedevice of FIG. 42, and a ceramic boat 52 f for accommodating fullerenemolecules was set in the quartz tube 52 b. Within this boat were chargedfullerene molecules (C₆₀) purified on sublimation. As this ceramic boat52 f was approached to the furnace core, an argon gas was supplied fromthe gas bomb 51 into the quartz tube 52 b.

In general, fullerene is said to be stable in an argon gas atmosphere.On continuous operation at 800° C. for four hours, a carbonaceous thinfilm as that obtained in Example 1 was formed on the quartz substrate 50e. The Raman spectrum, TOF-MS and the electrical conductivity weremeasured of the carbonaceous thin film and results similar to those ofExample 1 were obtained.

After cooling the electrical furnace 52, samples left in the g52 f werechecked. It was found that fullerene was decomposed and a smallgraphitic structure was generated.

Another carbonaceous thin film was prepared by thermally decomposingethanol in place of toluene of Example 1. The carbonaceous thin filmproduced was in no way different from that obtained in Example 1. Thisindicates that film forming is not dependent on the sort of the carbonmaterial (organic compound).

EXAMPLE 16

A fullerene vapor-deposited film was formed to a film thickness of 1000Å on a quartz substrate. The specific gravity of the film was set to 1.6on a film thickness monitor. This thin film was set in a quartz tube ofthe device shown in FIG. 42. After an argon gas was charged into thetube, the latter was installed in an electrical furnace and thetemperature was raised to 800° C. The electrical furnace was maintainedat 800° C. fir three hours and then was allowed to cool.

As a result, a carbonaceous thin film was formed on the fullerenevapor-deposited film on the quartz substrate. In distinction from thecarbonaceous thin film obtained in Examples 1 or 15, the presentcarbonaceous thin film was inferior in adhesion to the fullerenevapor-deposited film or to the quartz substrate, and showed the tendencyto be brittle.

EXAMPLE 17 Plasma Polymerization of a C₆₀ Vapor-Deposited Film

In the present Example, a C₆₀ vapor-deposited film on the C₆₀ polymerwas processed in Ar plasma to a C₆₀ polymer.

Formation of Fullerene Polymer Film

As fullerene C₆₀ molecules, as a starting material, a commerciallyavailable product was used. This C₆₀ could be prepared as follows: Usinga known device, arc discharge by a DC of 150 A was carried out in anhelium atmosphere of 100 Torr, with a graphite rod 10 mm in diameter and35 cm in length. After the graphite rod was substantially vaporized toyield a fullerene containing soot, the polarities of the two electrodeswere reversed and deposits such as nano-tubes formed on the inherentnegative electrode were further vaporized to soot.

The soot deposited in the water-cooled reaction vessel was recovered andextracted with crude toluene which then was rinsed with hexane, driedand purified on sublimation in vacuum. The fullerene molecules, thusproduced, were subjected to time-of-flight mass spectrometry (TOF-MS).It was thus found that the fullerene molecules contained C₆₀ and C₇₀ ata rate of approximately 9:1.

Then, using the apparatus shown in FIG. 8 or 38, a C₆₀ thin film,controlled to a film thickness of 20 Å, was formed on a siliconsubstrate at 4×10⁻⁶ Torr, by sublimating and evaporating powders of C₆₀,to form a thin C60 film, controlled to a film thickness of 20 Å, as theevaporated film thickness was measured using a film thickness meter. TheC₆₀ powders, set on a molybdenum boat, were heated gradually toapproximately 600° C. for degassing and evaporated at a highertemperature.

The evaporated film then was exposed to an Ar plasma of 0.1 Torr in anRF reaction vessel of plan-parallel plates started at 13.56 MHz. Eachsample of the C₆₀ thin film was maintained at 50° C. andplasma-processed at 30 W for four hours and at 50 W for thirty minutesto produce C₆₀ polymer films.

Raman Spectroscopy

The C₆₀ molecule shows 10 active modes in the Raman spectrum. Thestrongest line is observed at 1469 cm⁻¹. The Ag(2) pentagonal pinch mode(C—C single bond stretching) is the most sensitive to probe thepolymerization. Because of the polymerization, a shift of this mode isobservable and several new Raman lines are activated due to the loss ofmolecular symmetry. The shift has been used as a qualitative as well asquantitative measure of the polymerization. A downshift of 10 cm⁻¹ waspredicted theoretically for the C₆₀ dimer and trimer. A shift of about20 cm⁻¹ was predicted for longer polymers.

The Raman spectra of the processed films are shown in FIG. 1. The Ag(2)pentagonal pinch mode shifts in comparison to C60 by 4 to 5 cm⁻¹,respectively.

XPS

FIG. 58 shows the normalized XPS C 1s spectra. The C 1s binding energiesof the evaporated C₆₀ film and the plasma processed films weredetermined to be 284.9, 284.8 (30 W) and 284.7 eV (50 W). The full widthof half magnitude (FWHM) of the C 1s peak of the processed thin filmsincreased about 0.2 eV to 1.0 eV compared to 0.8 eV of the evaporatedfilm. Moreover, the shape of the C 1s becomes asymmetric to higherbinding energies. The calculated chemical shifts of the C 1s bindingenergy of +3 eV per four-membered ring in C₆₀ polymers with respect tothe isolated C₆₀ molecule explains only partially the differences in thespectra. On the other hand, 13 (30 W) and 15 at % (50 W) oxygen werefound by XS. The rather high overall FWHM's (2.7 and 2.5 eV) measuredfor the O 1s peaks indicates that different molecular and atomic oxygenspecies are superimposed.

FIG. 59 shows the peak analyses of C 1s of the plasma processed films.Peaks were found at 284.8 (284.7), 286.2 (286.1) and 288.7 (288.6) eV.The subpeaks correlate to C—O, C—O—O and C═O superimposed by shake-upfeatures.

FIG. 46 illustrates the expanded region covering the C 1s shake-upsatellites. Five bands were separated from C60 by high-resolutionphotoelectron spectroscopy at 1.8, 2.9, 3.7, 4.8 and 5.9 eV relative tothe C 1s binding energy. Three of these peaks were resolved for theevaporated C60 thin film, but not the peaks at 2.9 and 4.8 eV. Theobservation of the shake-up satellites of the plasma processed films issomewhat problematic because they are strongly superimposed by theemission from oxidized carbon species.

FIG. 61 shows the XS valence band spectra of the evaporated C60 film andthe plasma processed films. It is apparent that the peaks of the plasmaprocessed becomes broader and reduced in intensity. In addition to thecarbon states, the O2s peak appears at about 27 eV.

TOF-MS

FIGS. 62 and 63 show the TOF-MS spectra of the plasma processed films.In the spectra occur peaks in the mass range of about 1440, which areattributable to fullerene polymer. Also, the C₆₀ structure is retained.

The results of Raman, XPS and TOF-MS confirm that the plasma processingof evaporated C₆₀ films resulted in polymerized C₆₀. The describedmethod opens a new route to polymerize C₆₀ by plasma.

EXAMPLE 18 Preparation of Solar Cell and Its Physical Properties

For preparing a structure shown in FIG. 1, a carbonaceous thin film wasformed by a film-forming device shown in FIG. 56. This film formingdevice is made up of a simple type organic solvent gas bubbler 50, a gasbomb 51 for supplying a carrier gas thereto, and a simple typeelectrical furnace 52 for pyrolysis of the organic solvent gas. A needlevalve 53 for flow duct adjustment is provided in each of the flow ductbetween the gas bomb 51 and the organic solvent gas bubbler 50 and theflow duct between the gas bomb 51 and the electrical furnace 52.

The electrical furnace 52 has a furnace core 30 mm in diameter and aheater 52 b within which a thermocouple 52 d for connection to anexternal heater temperature controller 52, and a quartz substrate (glasssubstrate) 52, corresponding to the substrate 1, directly above thecontroller 52 c, are set for assuring correct film-forming temperatureof the quartz substrate 50 e. Meanwhile, a relay circuit for PID controlwas operated in unison for temperature control of the quartz substrate50 e. With the film-forming device, constructed as described above, isable to deposit a carbonaceous thin film with a temperature error lessthan 1° C.

The temperature of the electrical furnace 52 was set to 800° C. Afterintroducing the quartz substrate 52 e into the quartz tube 52 b, anargon gas, with a purity of 99.999%, was introduced from a gas bomb 51into the quartz tube 52 b to fill the inside of the tube with the argongas.

When the inside of the quartz tube 52 b is completely the argon gasatmosphere, and the temperature has reached 800° C., the toluene gas wasstarted to flow into the inside of the quartz tube 52 b through theorganic solvent gas bubbler 50. The flow velocity of the toluene gas,introduced into the organic solvent gas bubbler 50, was maintained at 50ml/min.

After continuing gas bubbling for 30 minutes, only the argon gas wasallowed to flow into the quartz tube 52 b, and the electrical furnace 52was cooled gradually. After confirming that the electrical furnace 52was cooled substantially to room temperature, the quartz substrate 52 ewas taken out of the quartz tube 52 b. On the surface of the quartzsubstrate 50 e was formed a thin carbon film presenting a mirrorsurface.

On the carbon thin film, a C₆₀ polymer film was formed, as explained inconnection with Example 1. The junction structure of the carbon thinfilm and the fullerene polymer film, thus fabricated, is a structureuseful for isolating the carrier generated on light illumination, suchthat, if the structure is used in a compound structure of, for example,a glass substrate—ITO electrode—carbon thin film—fullerene thinfilm—aluminum electrode, it is particularly useful for a solar cell.This structure has desirable properties, as may be seen from FIG. 26showing I-V characteristics on light illumination thereon.

What is detrimental in this case is that the electrically conductivityof the light-transmitting electrode is impaired when forming a carbonthin film on a light-transmitting electrode formed e.g., of ITO.

For avoiding this problem, a compound structure such as a glasssubstrate—thin gold electrode—thin carbon film—fullerene polymerfilm—aluminum electrode is preferably used. This compound structureoperates as a solar cell, as may be seen from the I-V characteristicsbefore and after light illumination. In order to provide a compoundstructure optimum for this application, it is necessary to scrutinizeinto variable factors, such as band gap of the carbon thin film,thickness of the fullerene thin film or the Fermi surface level of theelectrode material.

EXAMPLE 19 Preparation of Gas Sensor and its Performance

On a complex structure comprising a substrate—carbonaceous thinfilm—fullerene polymer film, prepared as in Example 18, a comb-shapedgold electrode was further formed thereon to check into the function asa gas sensor.

As result, electrical conductivity was noticed to be clearly changed,e.g., increased, against water, acetaldehyde, formaldehyde, ammonia orformic acid. This phenomenon was similarly noticed when the combelectrode was directly mounted on the carbonaceous thin film presentinga smooth surface, such that a clear distinction was observed from a casewhen a structure comprising only an electrode without provision of thecarbonaceous thin film was used as a reference.

Meanwhile, the carbonaceous complex structure according to the presentinvention, having the above-described basic structure, may be modifiedas to the material or the forming method or layering sequence of therespective layers, insofar as the meritorious effect of the invention ismaintained. In addition, the layered structure may be varied, such that,for example, each constituent layer may be subdivided into plurallayers, or the thickness of each layer may be designed optionally.

What is claimed is:
 1. A carbonaceous complex structure comprising alayered set of a substrate, a carbonaceous thin film and a fullerenepolymer thin film.
 2. The carbonaceous complex structure according toclaim 1 wherein said carbonaceous thin film and the fullerene polymerthin film are layered in this order on a smooth surface of saidsubstrate.
 3. The carbonaceous complex structure according to claim 2wherein said smooth surface of said substrate has a roughness Ra of notlarger than 1 μm.
 4. The carbonaceous complex structure according toclaim 1 wherein a first electrode is on the substrate, said carbonaceousthin film is on the first electrode, said fullerene polymer thin film ison the carbonaceous thin film, and a second electrode is on thefullerene polymer thin film.
 5. The carbonaceous complex structureaccording to claim 4 wherein said substrate and the first electrode aretransparent.
 6. The carbonaceous complex structure according to claim 1wherein said carbonaceous thin film and a pair of electrodes are layeredin this order on said substrate and wherein said fullerene polymer filmis formed at least between said electrodes.
 7. The carbonaceous complexstructure according to claim 1 wherein said carbonaceous thin film isformed by thermal decomposition of an organic compound.
 8. Thecarbonaceous complex structure according to claim 1 wherein saidfullerene thin film is a fullerene polymer film or a fullerenevapor-deposited film.
 9. The carbonaceous complex structure according toclaim 8 wherein said fullerene polymer film is a film polymerized onillumination of electromagnetic waves.
 10. The carbonaceous complexstructure according to claim 9 wherein said fullerene polymer film is apolymerized film of said vapor-deposited film formed to a pre-setthickness.
 11. The carbonaceous complex structure according to claim 9wherein said fullerene molecules are C₆₀ or C₇₀ or a mixture thereof andwherein said electromagnetic waves are RF plasma, UV rays or an electronbeam.